Stable ethylsilicate polymers and method of making the same

ABSTRACT

Ethylsilicate polymers and a method of making, specifically ethylsilicate polymer binders with reduced levels of regulated volatile organic compounds (VOCs) for use in the coatings industry and casting industry, and more specifically to stable, fast cure ethylsilicate polymer binders with low levels of regulated VOCs.

CROSS REFERENCE TO RELATED APPLICATIONS

This U.S. patent application claims the benefit of and priority to U.S.Provisional Patent Application Ser. No. 62/080,596 filed Nov. 17, 2014,the entire disclosure of the application being considered part of thedisclosure of this application, and hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention is directed to ethylsilicate polymers,specifically ethylsilicate polymer binders with reduced levels ofregulated volatile organic compounds (VOCs), and more specifically tostable, fast cure ethylsilicate polymer binders with low levels ofregulated VOCs.

BACKGROUND FOR THE INVENTION

Ethylsilicate polymers and ethylsilicate binders are used in a varietyof applications in various industries. Common uses include coatings,sealants, consolidents, and other uses in the investment castingindustry. Ethylsilicate binders are typically mixed into other productsfor use in commercial and industrial applications. For example, in thecoatings industry, the ethylsilicate binder may be mixed with othermaterials to create an inorganic zinc-rich primer for coating metalsagainst corrosion or before application of paint. In the castingindustry, ethylsilicate binders are mixed in with other materials toform the casting material into a hardened ceramic material.

Traditional ethylsilicate binders include various VOCs that are releasedduring the application and use of the product and while the productcures. Many of the VOCs included in traditional ethylsilicate bindersare regulated by various governmental agencies, such as theEnvironmental Protection Agency in the United States of America. In mostethylsilicate polymers the majority of regulated VOCs come from theethanol or other alcohols, and the solvents that are typically used tokeep the silica from gelling during manufacture, transportation, storageand use. For example, in the coatings industry, ethylsilicate binderswhen used in inorganic zinc-rich primers generally include a ketone oran ether as a solvent, such as at least one of methyl n-amyl ketone(MAK), dipropylene glycol monomethyl ether (also known as glycol etherDPM) and ethanol, which are subject to various VOC regulations. Thereare many other regulated solvents. The ethanol, MAK, and DPM are alsocommon in ethylsilicate polymers in the investment casting industry.These ethylsilicate binders, which include the above identifiedchemicals and solvents, which are regulated as VOCs, are well known andproduce products with long-term stability, easy manufacturing processes,high product performance, consistent product quality, and easytransportation and storage. As these ethylsilicate polymer binders incommon use generally use at least one of the above regulated solvents,and include ethanol, when they are used in commercial or industrialapplications, the user, whether as a value added manufacturer or an enduser, typically must monitor the amount of VOCs included in the productand the release of the regulated VOCs and comply with variousrestrictions on their application and use. If a user exceeds specifiedlevels, the user must take steps to mitigate which may be costly andrequire substantial time and effort to ensure compliance with variousregulations. As such, any reduction in regulated VOCs, in the endproduct, even if the ethylsilicate polymer is only a part of the endproduct, may save the user substantial costs, time and effort.

As many regulations regarding VOCs regulate such VOCs by measuring bywhat is in the product at the time of shipment, the use of ethylsilicatebinders including regulated VOCs, in addition to any ethanol created oradded during the manufacturing process, adds complexity and expense forthe user, if the regulated VOCs exceed the regulated thresholds.Therefore, many users of ethylsilicate polymers desired reducedregulated VOC products. However, as the industries where ethylsilicatepolymers are used are typically highly technical with strict performancerequirements, any reduction in performance characteristics with aproduct having lower regulated VOC levels would be unacceptable.

Some manufacturers have attempted to use water-based solvents that donot include regulated VOCs in place of solvents containing regulatedVOCs in ethylsilicate polymers or binders in order to reduce the amountof regulated VOCs. First, changing the solvents alone does not eliminateregulated VOCs, as the product still includes ethanol and otheralcohols. However, these known substitute solvents, particularly waterbased solvents when used in ethylsilicate polymer binders, havesubstantial performance, longevity and other issues and have not beenadapted by industry. More specifically, most ethylsilicate polymerbinders have a natural tendency to gel or precipitate out of thesolvent, making them generally unstable, particularly during storage,transportation, and subsequent use to create other products. In makingethylsilicate polymers, the manufacturer is constantly making sure theproduct does not gel or precipitate out of solution, as any minor changein formulation generally causes these negative results. As such, nosolvent substitution has had commercial acceptance because the resultingethylsilicate polymer had substantial reduced performancecharacteristics. In particular, water-based solvents createethylsilicate binders that are not stable, both during the manufacturingprocess as well as during transportation and storage. In addition, asmany users combine the ethylsilicate polymer with other materials toform a final product. Ethylsilicate polymers in water-based solvents aretypically unstable, as they have been found to react with many othermaterials causing the silica to gel or precipitate out. Specificproblems with ethylsilicate polymers using water-based solvents includea tendency to gel, which makes them unusable for most desiredapplications. Temperature changes during transportation and storage ofthe product are also problematic in ethylsilicate binders formed withwater-based solvents. Even if the solvent is not water-based,manufacturers have not to date found a solvent with low to no regulatedVOCs that may be substituted for the typical MAK or glycol ether DPMsolvents that retain substantially similar performance characteristics.Currently, all solvent substitutions for these traditional solvents,whether water-based or not, have not been able to provide the long termstability, consistent quality and consistent performance considerationsand furthermore are especially not stable during use, temperaturechanges, transportation, and subsequent use into a final product. Morespecifically, it has been found that solvent substitutions, whetherwater-based or not, tend to cause the ethylsilicate materials to gelwhich makes them unusable for the desired applications. With somesolvents, the ethylsilicate material may even suddenly gel during themanufacturing process creating substantial problems, and most solventsubstitutions at a minimum cause the ethylsilicate polymer to partiallygel, which is also unacceptable and creates numerous problems, includingprecipitation of the silica out of the material, all of which makes theproduct unfit for its intended purpose. These problems may even ruin theequipment used with ethylsilicate polymer under certain conditions.

In view of the above issues, there is a need for an ethylsilicatepolymer binder with low or reduced regulated VOCs which is highly stableduring the manufacturing process, transportation, storage, and finalpreparation into an end use product, including contributing to stablestorage and use of such end use product, with consistent, repeatable andhigh performance characteristics during use or application by theultimate user. Having non-regulated chemicals as solvents or an overallproduct with reduced regulated VOC levels may allow the end user toavoid otherwise necessary and expensive regulatory compliance stepsrequired by existing ethylsilicate polymer binders. Even if theethylsilicate binder still includes some regulated VOCs such as ethanol,the reduction in VOCs may allow for reduced regulatory compliance aswell as reduction in the time-consuming and expensive steps in complyingwith certain regulatory requirements as compared with products havingregulated VOCs. To date, no ethylsilicate polymer binder having low orreduced amounts of regulated VOCs is available with acceptable orimproved performance characteristics.

SUMMARY OF THE INVENTION

The present invention is directed to ethylsilicate polymers, preferableethylsilicate polymers with low levels of regulated volatile organiccompounds (VOCs), more specifically to stable, fast-curing ethylsilicatepolymer binders with reduced levels of regulated VOCs. In addition, thepresent invention provides a long-term stable binder that has reducedVOCs and substantially eliminates or reduces solvents that are regulatedfor VOCs, while yet having the similar or improved performancecharacteristics. In addition, surprisingly, the resulting ethylsilicatepolymer binder with the new solvents of the present invention even has afaster cure time than prior art ethylsilicate polymer binders that usecommon solvents having regulated VOCs, such as MAK and glycol ether DPM,and yet has much lower regulated VOCs.

The VOCs for a particular product are calculated as they are shipped andwhen such product is put into subsequent products, the end product mayinclude other products also containing components subject to VOCregulations. Therefore, any particular input product having lowerregulated VOC levels may provide benefits to a manufacturer who uses thematerials in producing additional products as well as the ultimate enduser of the product. For example, in the coatings industry,ethylsilicate polymer binders are used to create primers. In theinvestment casting industry, the ethylsilicate polymer binders are usedto create a hardened ceramic material. The manufacturer as well as theultimate end consumer must account for all input products subject to VOCregulations, and ensure that the particular product is under regulatorylimits, not subject to such regulations or if subject to suchregulations, comply with certain costly and time-consuming regulatoryrequirements regarding the release of VOCs including various capture andmitigation protocols.

The present invention reduces regulated VOCs in ethylsilicate binders bysubstituting a propylene carbonate, oxsol, tertiary butyl acetate, orcombination thereof, in place of the commonly used solvents, such asdipropylene glycol methyl ether or the methyl amyl ketone solvents thatare regulated for VOCs. Because ethylsilicate polymer binders are knownto be very unstable, any variation in the manufacturing process or anysubstation of chemicals typically causes failure of the product orreduced performance characteristics. In view of the above problems, amanufacturer is not able to simply substitute in any solvent that is notregulated into the process in place of MAK or DPM. Instead, the presentinvention has developed both a novel and unique process for forming theethylsilicate polymer and substitute chemicals that are not regulatedfor VOC levels and yet maintains desired performance characteristics. Inaddition, it has been found that a single substitution of a solvent inplace of the MAK or DPM did not function or provide a stable product,and using the same process to make an ethylsilicate polymer product asone made using as MAK or DPM as a solvent unexpectedly did not providethe resulting product with the desired performance characteristics.While traditionally ethylsilicate polymer binders may be formed withonly MAK, only DPM, or a combination of thereof to provide a stableproduct, it has been found that any substitution with exempt solventcaused the product to gel during the manufacturing process or duringstorage and transportation. As such, the product was never able to beused as desired by various types of users. To avoid gelling during themanufacturing process, and during storage and transportation, as well asuse by value added manufactures or the ultimate end user, the inventorshave developed new formulations and methods, such as using propylenecarbonate, and adding the propylene carbonate as a solvent beforehydrolysis. It has also been found that for the best performancecharacteristic and high stability, as described below, after hydrolysisanother solvent such as oxsol or tertiary butyl acetate should be used.The combination of propylene carbonate before hydrolysis and at leastone of oxsol or tertiary butyl acetate after hydrolysis, a stableethylsilicate polymer binder may be formed with high-performancecharacteristics and surprisingly, as described below, an improvedfast-cure ethylsilicate polymer binder, with improved drying times inend use products.

The present invention is generally directed to a polyethylsilicatecomposition having generally 18-50% by weight SiO2 based on the totalcomposition weight; 0-60% by weight alcohol based on the totalcomposition weight; and a positive amount of solvent, wherein saidsolvent forms up to 25% by weight, based on the total compositionweight, and wherein said solvent comprises at least one of propylenecarbonate, tert-butylacetate, or parachlorobenzotrifluoride; and whereinsaid solvent and said alcohol in combination form 5-70% by weight, basedon the total composition. The composition in generally hydrolyzed in anamount of 55-90%, and any alcohol or ethanol produced during hydrolysismay be left in to stabilize the final product, but is expected to atleast be partly stripped out to reduce regulated VOCs, as most alcohols,including ethanol are regulated VOCs. It is expected that ethanol willform the majority (greater than 50%) of the alcohol, and morespecifically that the alcohol will be substantially ethanol, that isonly minor amounts of alcohols are present, as one skilled in the artwould recognize that any alcohol formed from chemical reaction generallyincludes minor amounts of other alcohol.

The solvent and ethanol are expected to be 10-55%, preferably 16-45% andmore preferably 35-50% by weight, based on the weight of the totalcomposition, for most binders of the present invention when used withzinc rich primers in the coating industry. In comparison, when thepresent invention is used in the castings industry, such as a binderused to harden investment casting, the solvent and ethanol are typically10-70%, preferably 30-68%, and more preferably 40-60% by weight, basedon the weight of the total composition. Notwithstanding the foregoing,as some of the ethanol may be stripped out, it is expected that ethanolwill typically form less than 60%, preferably less than 45%, and morepreferably less than 40% by weight, based on the weight of the totalcomposition. Removal of ethanol or other alcohols reduces the regulatedVOCs. While the present invention includes a binder with no or at mosttrace levels of alcohol (less than 0.5% by weight), it is expected thatmost formulations will include some ethanol as it is generally helpfulin stabilizing the composition, and in the casting industry makesworking the product when added to refractories easier, typically 10-40%by weight ethanol, based on the weight of the total composition.

As stated above, most binders used in the coatings and castingindustries include at least one of methyl amyl ketone, or dipropyleneglycol methyl ether, in addition to high levels of ethanol, such as morethan 45%, typically more than 50% and likely more than 55% by weight ofa combination of the above items, based on the total weight of thecomposition, which lead to the up to 80% by weight regulated VOCs, basedon the total weight of the composition. In view of the above, most ofthe binders of the present invention are free from or include traceamounts (less than 0.5% by weight of the total composition) of methylamyl ketone and dipropylene glycol methyl ether. Notwithstanding theforegoing, some binders may include small amounts of methyl amyl ketoneand/or dipropylene glycol methyl ether to obtain certain performancecharacteristics. As such, the composition of the present inventionincludes a solvent having less than 10%, preferably less than 5% andmore preferably less than 3% by weight of methyl amyl ketone, based onthe weight of the total composition, and less than 7.5%, preferably lessthan 5% and more preferably less than 3% by weight of dipropylene glycolmethyl ether, based on the weight of the total composition. Incompositions that include at least one of methyl amyl ketone ordipropylene glycol methyl ether, they occur at most individually or incombination in an amount of 1-3% by weight, based upon the weight of thetotal composition. However, as stated above, most of the compositionsclaimed are essentially free of said methyl amyl ketone and saiddipropylene glycol methyl ether.

The solvent of the composition, while present in a positive amount, mayinclude generally 0-25%, by weight of said propylene carbonate, 0-25% byweight of said tert-butylacetate, or 0-25% by weight of saidparachlorobenzotrifluoride, each individually based upon the weight ofthe total composition. If the solvent includes propylene carbonate, itgenerally includes 5-15%, preferably 5-10% by weight of said propylenecarbonate, based on the weight of the total composition. If the solventincludes tert-butylacetate, it generally includes 5-18%, preferably8-15% by weight of said tert-butylacetate, based on the weight of thetotal composition. If the solvent includes parachlorobenzotrifluoride,it generally includes 5-15%, preferably 8-15% by weight of saidparachlorobenzotrifluoride, based on the weight of the totalcomposition. Of course, if the solvent includes two or more, each oneindividually may appear in a smaller amount than the above statedranges, yet in combination would form at least 3-40%, preferably 4-30%,and more preferably 4-25% and yet more preferably 4.5-24% by weight,based on the weight of the total composition. As illustrated in some ofthe tables, the solvent in some binders includes both propylenecarbonate and said tert-butylacetate, or both propylene carbonate andparachlorobenzotrifluoride. In the event the solvent includes propylenecarbonate and tert-butylacetate, the solvent includes 10-25% by weightof the combination of said propylene carbonate and saidtert-butylacetate, based on the total weight of the composition. Inaddition, where the solvent includes 10-25% by weight of the combinationof said propylene carbonate and said tert-butylacetate, based on thetotal weight of the composition, the propylene carbonate forms 10-20% byweight and the tert-butylacetate 5-15% by weight, each based on theweight of the total composition for use in the castings industry,although such binders could be used in the coatings industry. Incomparison, for the coatings industry, although the resulting bindercould also be used in the castings industry, where the solvent includes10-25% by weight of the combination of said propylene carbonate and saidtert-butylacetate, based on the total weight of the composition, thepropylene carbonate forms 3-12% by weight and the tert-butylacetateforms 7-14% by weight, each based on the weight of the totalcomposition. In addition, for certain binders or compositions where thesolvent includes both propylene carbonate and tert-butylacetate, thesolvent generally includes 5-6% by weight of said propylene carbonateand 13-14% by weight of said tert-butyl-acetate each based on the weightof the total composition. For the binders or compositions including bothpropylene carbonate and tert-butylacetate, the alcohol generally forms35-40% by weight, based on the weight of the total composition. Theabove compositions, including both propylene carbonate andtert-butylacetate, when used as binders in the coatings industry havebeen found that when used in connection with zinc rich coatings, theyprovide an improved binder with a much faster cure time, such thatsurprisingly the resulting coating is capable of passing a MEK 50 rubtest in between six and eight hours after application of a zinc richcoating formed of the ethylsilicate as a binder with zinc dust orparticles and refractories. For these coatings, the compositions formingthe binders generally include alcohol 35-40% by weight, solvents 18-20%by weight, which in turn include 5-6% by weight of said propylenecarbonate and 13-14% by weight of said tert-butyl-acetate, each basedupon the weight of the total composition. In addition, the ethylsilicatecomposition is hydrolyzed and the propylene carbonate is added before orduring hydrolysis and the tert-butyl-acetate is added after hydrolysis.The source of the SiO₂ may be either a colloidal silica sol or acondensed silica solution.

The present invention is also generally directed to a polyethylsilicatecomposition comprising: 18-80% by weight of SiO₂, based on the totalweight of the composition, an acid; an alcohol; a propylene carbonate inan amount of up to 30% by weight, based on the weight of the compositionand wherein said alcohol and said propylene carbonate in combinationform less than 70% by weight, based on the total weight of thecomposition. The composition is hydrolyzed in an amount of 55-90%, andthe propylene carbonate is added before or during hydrolization of thecomposition. It is believed that the propylene carbonate is helpful instabilizing the composition during hydrolysis. The composition mayfurther include tert-butylacetate, which is added after hydrolization inan amount of up to 25% by weight, based on the weight of thecomposition. If the tert-butylacetate is added before hydrolization itis typically consumed. The composition may also includeparachlorobenzotrifluoride in an amount of up to 25% by weight, based onthe weight of the composition. In some compositions, the composition mayincluding in combination, tert-butylacetate, parachlorobenzotrifluorideand propylene carbonate in an amount of 5-40% by weight, based on theweight of the total composition.

The present invention is also directed to a method of forming apolyethylsilicate composition and wherein said method includes the stepsof: adding ethanol, an acid and a silica source to a reactor; heatingthe reactor after said step of adding; adding an ethylsilicate source tothe reactor to initiate a hydrolysis reaction; and adding propylenecarbonate to the reactor after the hydrolysis reaction. The method mayfurther including the steps of adding parachlorobenzotrifluoride to thereactor after the hydrolysis reaction. In addition, the method mayinclude a step of stripping ethanol from the reactor. The silica sourceis expected to be a colloidal silica sol, but also could be a condensedsilica solution. In addition, the method may include the steps of addingpropylene carbonate before adding, during adding or both before andduring adding the ethylsilicate source,

The present invention is further directed to a method of forming apolyethylsilicate composition and wherein said method includes the stepsof: adding a silica source and a propylene carbonate to a reactor; andadding an ethylsilicate source to the reactor to initiate a hydrolysisreaction. The method may further include the step of addingtert-butylacetate to the reactor after said hydrolysis reaction. Inaddition, the method may include a step of adding additional propylenecarbonate after the hydrolysis reaction. The method may further includethe steps of adding a mineral acid to the reactor before the hydrolysisreaction, heating the reactor, including the silica source, propylenecarbonate, and acid, adding a solvent after the hydrolysis reaction,such as propylene carbonate, tert-butylacetate, andparachlorobenzotrifluoride.

The present invention may also be directed to a method of forming apolyethylsilicate composition and wherein said method includes the stepsof: adding ethanol, an acid and a silica source, and propylene carbonateto a reactor; heating the reactor after said step of adding; andhydrolizing the contents of the reactor. The hydrolysis reaction may beinitiated by adding water to the reactor. Of course, the reactor may beheated or cooled as needed during the method, and the silica source maybe a polyethylsilicate.

The invention will now be described in connection with the accompanyingtables.

DETAILED DESCRIPTION

The present invention is directed to ethylsilicate polymers and a methodof manufacturing ethylsilicate polymers, specifically ethylsilicatepolymer binders with reduced levels of regulated volatile organiccompounds (VOCs), and more specifically to stable, fast cureethylsilicate polymer binders with low levels of regulated VOCs.

The reduced regulated VOC ethylsilicate polymer of the present inventionis generally formed by substituting a propylene carbonate, oxsol,tertiary butyl acetate, or combination thereof in place of thedipropylene glycol methyl ether or the methyl amyl ketone. Bothdipropylene glycol methyl ether or the methyl amyl ketone are commonlyused as solvents and are regulated VOCs, and as such, any of suchsolvents remaining after production in the ethylsilicate polymer productcontribute to the calculated amount of regulated VOCs in theethylsilicate product. Any reduction in the level of regulated VOCs isbeneficial to the users, such as value added manufacturers or end users.The present invention has been found to form a high performance, reducedregulated VOC ethylsilicate polymer, with the option for a faster curewith propylene carbonate, oxsol, tertiary butyl acetate, or combinationthereof in place of the dipropylene glycol methyl ether or the methylamyl ketone.

Because prehydrolyzed ethyl polysilicate binders are typically unstable,it has been found that any variation in the manufacturing process orsubstitution of chemicals creates an unstable product. Therefore, evenafter substantial effort to create products having non-regulatedsolvents, which are in the present invention propylene carbonate, oxsol,tertiary butyl acetate or combination thereof, it was found that simplesubstitution in place of the dipropylene glycol methyl ether or themethyl amyl ketone solvents in the same amounts and using the sameprocess caused reduced performance characteristics or making a productthat was completely unusable to customers. In addition, whiletraditional ethylsilicate polymer binders may be formed with only MAK,or only DPM, the present invention instead uses propylene carbonate as asolvent. In addition, it has been determined that for best performancecharacteristics that the polypropylene carbonate should be added beforehydrolysis to stabilize the reaction during the hydrolysis by preventingundesirable gelation. It is believed that the reaction is stabilized byadding propylene carbonate as a solvent before hydrolysis stabilizes thereaction during the hydrolysis and prevents undesirable gelation duringhydrolysis. While additional propylene carbonate may be added afterhydrolysis, it has also been found that for the best performancecharacteristic in high stability for ethylsilicate binders used asprimers and other materials, as described below, after hydrolysis asolvent such as oxsol or tertiary butyl acetate, or combination thereofbe used, which provides additional stabilization of the material.However, it has been found that for ethylsilicate polymers and bindersused in investment casting, tertiary butyl acetate does not perform welland oxsol is too expensive and slow to set up, such that any additionalsolvent added after hydrolysis is a different low VOC solvent or morepropylene carbonate. By using the combination of propylene carbonatebefore hydrolysis and at least one of oxsol or tertiary butyl acetateafter hydrolysis, a stable prehydrolyzed ethyl polysilicate binder withhigh-performance characteristics and as described below, surprisinglyimproved drying times may be formed.

As described below in Table 1, the prehydrolyzed ethyl polysilicatesfrom broadly 10-80% by weight. However, in the castings field, binderstypically have a broad range of 20-80% by weight, and in the field ofprimers a broad range of 30%-75%. The preferred ranges for castings is50-70% by weight prehydrolyzed ethyl polysilicates, and in the primersfield 25-80% by weight prehydrolyzed ethyl polysilicates. The productVOCs by weight are 45-80% broadly, with castings field using productshaving product VOCs with 50-75% by weight, and preferred 55-75%, and inthe primers field, products having product VOCs with 50-75% by weight,typically 55-70% by weight and 50-60% by weight. The product may includenon-exempt or regulated solvents of Methyl Amyl Ketone (MAK); and 0-25%,preferable 5-20% and more preferably 10-15%; Dipropylene Glycol MethylEther (DPM) 0-20%, preferable 5-15%, and more preferably 5-10%, allreferences by weight percent of the total product. In addition, theabove list of MAK, DPM and the like are examples and are not all of theregulated solvents currently used in making ethylsilicate polymers. Asall of these are chemicals that are regulated for release of VOCs, theincrease in regulated VOCs may be clearly seen. While some binder havebeen used in the industry with 10-20% by weight VOCs, these binders arevery high in SiO₂ content and are very expensive. In addition, the VOCsare regulated VOCs, and these existing low VOC binders have very limiteduses with the SiO₂ content. For example, these low VOC binders are notable to be used with refractories, because there is not enough viscosityand therefore does not do well in the castings field or primers field,and they do not have a long shelf life and are hard to blend withoutgelling, as it is so highly hydrolyzed given the high SiO₂ content. Tosummarize, they are unstable, gel and are not able to be used in thefield, and their primary use is to be a base binder that is diluted withethanol or other alcohols or regulated solvents before being shipped tothe customer for use. Therefore, while these binders exist, they are notuseable in the industry as is, and when shipped have a VOC content afterdilution that is typically greater 45% by weight.

TABLE 1 Ranges Broad Narrow Preferred % % % Prehydrolyzed ethyl 20-8025-45 30-42 polysilicates Wt. % Product VOC Wt % 45-80 50-75 55-75(Total Non-Exempt Solvents Wt % including ethanol and other alcohols)Specific Gravity  .900-1.200  .940-1.150  .990-1.100 SiO₂ Wt. % 18-5020-40 25-35 Acidity Wt. % .01-.50 .15-.35 .20-.30 % Hydrolyzed 55-9060-85 65-80

As described below in Table 2, the resulting prehydrolyzed ethylsilicateproduct may include by weight percent of the resulting product 20-50%,preferably 25-45% and more preferable 30-42%; ethanol and other alcoholsat the time of shipment of 0-60%, preferable 25-50% and more preferably30-40% by weight of the total product at the time of shipment (for thecastings industry 10-60% (due to the high ethanol content or othersolvent required when working with refractories), preferably 25-50% andmore preferably 30-40% by weight of the product at time of shipment)(for the primers/coatings industry 0-40%, preferably 10-30%, and 15-20%by weight of the product at time of shipment); exempt or non-regulatedsolvents (VOCs not regulated) which may include Propylene Carbonate (PC)0-30%, 0-25% typical, preferable 5-15% and more preferably 5-10% byweight of the product at time of shipment; Tert-Butyl Acetate (TBA)0-30%, 0-25% typical, preferable 5-15% and more preferably 8-15%;Parachlorobenzotriflouride (PCBTF)—also known as Oxsol 100) 0-30%, 0-25%typical, preferable 5-15, and more preferably 8-15%; or at least one ofthe above, or a combination of at least two of the above, forming atotal of exempt or non-regulated solvents of 5-40%, preferable 10-25%and more preferably 16-23% by weight at the time of shipment. Inaddition, the product at the time of shipment will include 18-50%,preferable 20-40%, and more preferable 25-35% of silica (SiO₂) byweight. Other components of the prehydrolyzed ethyl polysilicateproduct, as prepared, generally include a mineral or organic acid, andin some binders colloidal silica occurring in 0-20%, preferable 5-15%,and more preferably 7-11% by weight at the time of shipment.

It is expected that a reduction of at least 5-10%, preferably 10-25% andmore preferable 20-45% of regulated VOCs will occur in the finalprehydrolyzed ethyl polysilicate product of the present invention. Inaddition, the prevent invention is capable of reducing the regulated ornon-exempt VOCs to 0% by weight of the overall product at the time ofshipment. However, in the castings industry, the regulated or non-exemptVOCs is expected to have a minimum of 15%, more likely 20% by weight ofthe final product at the time of shipment, due to casting binders havinga higher amount of VOCs in the prior art products, and in addition, someof the non-exempt solvents are not able to be used in the castingsindustry. For example, TAB is not able to be used in castings industryas it does not have the desired performance characteristics. Inaddition, the coatings or primers industry has traditionally had lowerregulated amounts of allowed VOCs than the castings industry, so thebinders used in the castings industry were already improved with lowerVOC levels, however due to regulations from governmental industries, itis expected that a greater reduction is required in VOC levels in thefuture. The present invention may in certain circumstances use regulatedor non-exempt solvents, such as MAK, DPM or the like 0-10%, preferably0-5% and more preferably 0-3% by weight of the product at the time ofshipment, to meet certain performance characteristics. However, thesebinders typically previously had 50% or more of these regulatedsolvents, and as such, the amount has been reduced by typically a factorof 10 or more, which is a huge reduction in such regulated VOCs.

TABLE 2 Ranges Broad Narrow Preferred % % % Prehydrolyzed ethyl 20-60 25-45  30-42  polysilicates Wt. % Product VOC Wt % 20-55  30-50  32-40 Specific Gravity .900-1.200 .940-1.150 .990-1.100 SiO₂ Wt. % 18-50 20-40  25-35  Acidity Wt. % .01-.50  .15-.35  .20-.30  % Hydrolyzed55-90  60-85  65-80  Total Non-Exempt Solvents Wt. % 0-60 0-50 0-40(including ethanol and other alcohols) Ethanol and other alcohols Wt %0-60 0-50 0-40 Total Exempt Solvents Wt. % 5-40 10-25  16-23  ReducedVOC Prehydrolyzed ethyl polysilicate Products Propylene Carbonate (PC)0-30 5-15 5-10 Tert-Butyl Acetate (TBA) 0-30 5-15 8-15Parachlorobenzotrifluoride (PCBTF) 0-30 5-15 8-15 (Oxsol 100)

A list of examples follows in various tables. These examples have beenfound to have acceptable performance characteristics, and as identifiedbelow, some of the examples were found not to be acceptable. Inaddition, 2-amino 2-methyl 1-proponal may also be used as a solvent, byitself, or in combination with the other identified solvents. It can beput in before, during or after hydrolysis. Of course, the desiredperformance characteristics may vary depending on the desiredapplication. For example, the LV4 and LV5 formulations in Tables 18 and19 are very desirable for use in the casting industry. In comparison,the LV1-LV3 formulations in Tables 3-6 as examples 1-10 and LV3.1 inTables 18 and 19 are very useful as binders for zinc oxide primers inthe coatings industry. The specific example number is provided in theleft column of the relevant tables, and specific examples may occur inmultiple tables. Table 3 provides exemplary input weights, and Table 4provides the same information by weight percent. The examples 11 and 21in the tables is labeled as “standard” because it is a typical industryethylsilicate polymer binder used with primers. The tables also includereferences to Silbond HT-28A, Silbond HT-33, Silbond HT-21.5PM, SilbondHT-25, and Silbond HT-30, with information regarding the silicon dioxidelevels and product VOC levels, for comparison, as these are existingbinders that use DPM, MAK or a combination thereof, and in the eventthat DPM or MAK is not used, such as in HT-21.5PM, H-25, and HT-30, veryhigh levels of ethanol are used, such as five to eleven times as muchethanol as compared to the HT-28A and HT-33 binders that use DPM andMAK. It should be noted that binders do exist that do not include MAKand DPM, however such binders have very high levels of ethanol, which isa regulated VOC, and as such are not reduced, low level or exempt VOCsbinders. Therefore, the invention is not simply directed to the removalof DPM and MAK, but also a binder that uses low levels of ethanol inaddition to not use (or using minor amounts) of DPM and MAK.

In Tables 3 and 4, the amount hydrolyzed, the percentage of VOC (byweight percent) and the amount of SiO₂ by weight percent as well as theatmospheric-aged shelf life stability of the product are shown. The sameexamples are then carried forward into Tables 5 and 6, which provide thefinal product formulations for the examples that go through the process.It should be noted that Examples 1-5 include no MAK or DPM, whileExample 6 includes reduced amounts of MAK and no DPM, which as statedabove is regulated for release of VOCs. Examples 7-10 include DPM, whichas stated above is regulated for release of VOCs, but no MAK. Example 10has reduced amounts of DPM and no MAK. Example 11 is an exemplarystandard prior art batch input, including full amounts of MAK and DPM.As seen in Tables 3-6, Example 11 includes by weight 50.5% chemicalsthat are regulated for VOC levels, however the amount of regulated VOClevels may fall as low as 35% in the Examples in Tables 3-6. In thelater tables with the LV4 and LV5 formulations or variations thereof,the ethanol amounts in the product may be minimized also creating lowVOC binders.

In Tables 3-6, the column headers mean the following: Colloidal Solmeans 50% sodium silicate dispersion; Sulfuric Acid means 93% technicalgrade sulfuric acid; DPM means dipropylene glycol methyl ether(non-exempt solvent); MAK means methyl amyl ketone (non-exempt solvent);PC means propylene carbonate (exempt solvent); PCBTF meansparachlorobenzotrifluoride (exempt solvent); TBA means tert-butylacetate(exempt solvent); Hydrolysis means a process used to reactethylsilicates with water; SiO₂ means theoretical silica dioxide contentas a percent by weight. As seen in Tables 5 and 6, the final product forall examples included about 31-34% by weight of SiO₂ and was 65.4%hydrolyzed.

TABLE 3 Low VOC LV-3 Batch Formulations by Weight CompositionDipropylene Glycol Methyl Ethyl Methyl Amyl Propylene SilicatesColloidal Sulfuric Ether Ketone Carbonate Blend Sol Acid (DPM) (MAK)(PC) Binder (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) 1 LV-3 PC-PC2728.5 537.6 10.6 569.0 2 LV-3 PC-OX 2728.5 537.6 10.6 179.8 3 LV-3PC-TBA 2728.5 537.6 10.6 179.8 4 LV-3 tBA-double PC 2728.5 537.6 10.6359.6 5 LV-3 PC-TBA mod. molar 2728.5 537.6 10.6 123.8 6 LV-3 PC-TBA-MAK2728.5 537.6 10.6 97.3 179.8 7 LV-3 DPM-TBA 2728.5 537.6 10.6 179.8 8LV-3 DPM-OX 2728.5 537.6 10.6 179.8 9 LV-3 DPM-PC 2728.5 537.6 10.6179.8 389.2 10 LV-3 PC-TBA-DPM 2728.5 537.6 10.6 79.8 279.8 11 3Standard 2728.5 537.6 10.6 179.8 389.8 tert Parachloro- Butylbenzotrifluoride Acetate Product Atmospheric (PCBTF) (TBA) HydrolysisSiO₂ VOC Stability Oxsol 100 (wt. %) (wt. %) % (wt. %) (wt. %) (months)1 65.4 33.56 35.8 3.0 2 389.2 65.4 33.56 35.8 3.0 3 389.2 65.4 33.5635.8 3.0 4 389.2 65.4 32.06 34.2 4.5 5 396.0 65.4 34.43 36.7 2.5 6 291.965.4 33.56 38.3 4.5 7 389.2 65.4 33.56 40.4 11.5 8 389.2 65.4 33.56 40.47.0 9 65.4 33.56 40.4 4.5 10 389.2 65.4 31.83 35.9 na 11 65.4 33.56 50.56.0+

TABLE 4 Low VOC LV-3 Batch Formulations Percent Composition DipropyleneGlycol Methyl Ethyl Methyl Amyl Propylene Silicates Colloidal Sulfuricether Ketone Carbonate Blend Sol Acid (DPM) (MAK) (PC) Binder (wt. %)(wt. %) (wt. %) (wt. %) (wt. %) (wt. %) 1 LV-3 PC-PC 70.96 13.98 0.2814.80 2 LV-3 PC-OX 70.96 13.98 0.28 4.68 3 LV-3 PC-TBA 70.96 13.98 0.284.68 4 LV-3 tBA-double PC 67.78 13.35 0.26 8.93 5 LV-3 PC-TBA mod. molar72.78 14.34 0.28 4.80 6 LV-3 PC-TBA-MAK 70.96 13.98 0.28 2.53 4.68 7LV-3 DPM-TBA 70.96 13.98 0.28 4.68 8 LV-3 DPM-OX 70.96 13.98 0.28 4.68 9LV-3 DPM-PC 70.96 13.98 0.28 4.68 10.12 10 LV-3 PC-TBA-DPM 67.28 13.260.26 1.97 7.63 11 3 Standard 70.96 13.98 0.28 4.68 10.12 Parachloro-Tertiary benzo- Butyl trifluoride Acetate Product Atmospheric (PCBTF)(TBA) Hydrolysis SiO₂ Wt. VOC Stability Oxsol 100 (wt. %) (wt. %) % (wt.%) (wt. %) (months) 1 65.4 33.56 35.8 3.0 2 10.12 65.4 33.56 35.8 3.0 310.12 65.4 33.56 35.8 3.0 4 9.67 65.4 32.06 34.2 4.5 5 7.79 65.4 34.4336.7 2.5 6 7.59 65.4 33.56 38.3 4.5 7 10.12 65.4 33.56 40.4 11.5 8 10.1265.4 33.56 40.4 7.0 9 65.4 33.56 40.4 4.5 10 9.60 65.4 31.83 35.9 na 1165.4 33.56 50.5 6.0+

TABLE 5 Low VOC LV-3 Final Product Formulations by Weight CompositionDipro- Para- pylene chloro- Glycol Methyl Propyl- benzo- Tertiary Col-Sul- Methyl Amyl ene Car- trifluoride Butyl Pro- Atmos- Poly- loidalfuric Ethanol Ether Ketone bonate (PCBTF) Acetate Hydrol- duct phericsilicates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO₂VOC Stability Binder (g) (g) (g) (g) (g) (g) (g) (g) (g) % (wt. %) (wt.%) (months)  1 LV-3 PC-PC 1622.6 268.8 10.6 1374.7 569.0 65.4 33.56 35.7 3.0  2 LV-3 PC-OX 1622.6 268.8 10.6 1374.7 179.8 389.2 65.4 33.56 35.7 3.0  3 LV-3 PC-TBA 1622.6 268.8 10.6 1374.7 179.8 389.2 65.4 33.56 35.7 3.0  4 LV-3 tBA- 1622.6 268.8 10.6 1374.7 359.6 389.2 65.4 32.06 34.2 4.5 double PC  5 LV-3 PC-TBA 1622.6 268.8 10.6 1374.7 123.8 396.0 65.434.00 36.2  2.5 mod. molar  6 LV-3 PC-TBA- 1622.6 268.8 10.6 1374.7 97.3179.8 291.9 65.4 33.56 38.3  4.5 MAK  7 LV-3 DPM- 1622.6 268.8 10.61374.7 179.8 389.2 65.4 33.56 40.4 11.5 TBA  8 LV-3 DPM-OX 1622.6 268.810.6 1374.7 179.8 389.2 65.4 33.56 40.4  7.0  9 LV-3 DPM-PC 1622.6 268.810.6 1374.7 179.8 389.2 65.4 33.56 40.4  4.5 10 LV-3 PC-TBA- 1622.6268.8 10.6 1374.7 79.8 309.4 389.2 65.4 31.83 35.9 na DPM 11 3 Standard1622.6 268.8 10.6 1374.7 179.8 389.2 65.4 33.56 50.5  6.0+

TABLE 6 Low VOC LV-3 Final Product Formulations Percent CompositionDipro- Para- pylene chloro- Glycol Methyl Propyl- benzo- Tertiary Col-Methyl Amyl ene Car- trifluoride Butyl Pro- Atmos- Poly- loidal SulfuricEthanol Ether Ketone bonate (PCBTF) Acetate Hydrol- SiO₂ duct phericsilicates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis Wt.VOC Stability Binder (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %)(wt. %) (wt. %) (wt. %) % (wt. %) (wt. %) (months)  1 LV-3 PC-PC 42.196.99 0.28 35.75 14.79 65.4 33.56 35.7  3.0  2 LV-3 PC-OX 42.19 6.99 0.2835.75 4.68 10.12 65.4 33.56 35.7  3.0  3 LV-3 PC-TBA 42.19 6.99 0.2835.75 4.68 10.12 65.4 33.56 35.7  3.0  4 LV-3 tBA- 40.31 6.68 0.26 34.158.93 9.67 65.4 32.06 34.2  4.5 double PC  5 LV-3 PC-TBA 42.47 7.08 0.2836.21 3.26 10.43 65.4 34.00 36.2  2.5 mod. molar  6 LV-3 PC-TBA- 42.196.99 0.28 35.75 2.53 4.68 7.59 65.4 33.56 38.3  4.5 MAK  7 LV-3 DPM-42.19 6.99 0.28 35.75 4.68 10.12 65.4 33.56 40.4 11.5 TBA  8 LV-3 DPM-OX42.19 6.99 0.28 35.75 4.68 10.12 65.4 33.56 40.4  7.0  9 LV-3 DPM-PC42.19 6.99 0.28 35.75 4.68 10.12 65.4 33.56 40.4  4.5 10 LV-3 PC-TBA-40.02 6.63 0.26 33.90 1.97 7.63 9.60 65.4 31.83 35.9 na DPM 11 3Standard 42.19 6.99 0.28 35.75 4.68 10.12 65.4 33.56 50.5  6.0+

As an example of a different amount of hydrolysis and SiO₂, Tables 7-10are included below. As may be seen from the Tables, the solvents usedcorrelate, such that Example 1 is similar to Example 12, and so on. Forease of reference a prior art Example 21 is included having both DPM andMAK. As may be seen in Tables 7-10, an additional step of stripping offthe ethanol and other alcohols occurs, which does not occur with theExamples 1-10 in Tables 3-6. Any inclusion of “na” in the table meansthat the data is not available, such as a study of the atmosphericstability was not completed or is in process, and should not be taken asmeaning not acceptable.

TABLE 7 Low VOC LV-2 Batch Formulations by Weight Composition Dipro-Para- pylene chloro- Glycol Methyl Propyl- benzo- tert Ethyl Col- Sul-Methyl Amyl ene Car- trifluoride Butyl Stable Sil- loidal furic EthanolEther Ketone bonate (PCBTF) Acetate Hydrol- EtOH Product Atmos- icatesSol Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO₂ Strip VOCpheric Binder (g) (g) (g) (g) (g) (g) (g) (g) (g) % (wt. %) (g) (wt. %)(months) 12 LV-2 2 × TBA 2093 584.6 7.8 800 515.0 80.7 32.97 1282 37.32.5 13 LV-2 2 × OX 2093 584.6 7.8 800 515.0 80.7 32.97 1282 37.3 4.5 14LV-2 2 × PC 2093 584.6 7.8 800 515.0 80.7 32.97 1282 37.3 2.5 15 LV-2PC-TBA 2093 584.6 7.8 800 154.3 360.7 80.7 32.97 1282 37.3 4.0 16 LV-2PC-OX 2093 584.6 7.8 800 154.3 360.7 80.7 31.20 1282 35.3 4.0 17 LV-2 2× 2093 584.6 7.8 800 308.6 360.7 80.7 31.20 1282 35.3 4.0 PC-TBA 18 LV-2PC-MAK 2093 548.6 7.8 800 389.2 154.3 80.7 31.80 1282 51.0 9.0+ 19 LV-22 × 2093 584.6 7.8 800 100.0 308.6 260.7 80.7 31.20 1282 38.7 naPC-TBA-MAK 20 LV-2 2 × 2093 584.6 7.8 800 125.0 308.5 360.7 80.7 29.891282 38.0 na PC-TBA-DPM 21 2 Standard 2093 584.6 7.8 800 154.3 360.780.7 32.97 1282 56.2 6.0+

TABLE 8 Low VOC LV-2 Batch Formulations Percent Composition Dipro- Para-Ter- pylene Pro- chloro- tiary Glycol Methyl pylene benzo- Butyl EthylCol- Sul- Methyl Amyl Car- trifluoride Ace- Hy- Pro- Stable Sil- loidalfuric Ethanol Ether Ketone bonate (PCBTF) tate drol- EtOH duct Atmos-icates Sol Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO₂ StripVOC pheric Binder (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt.%) (wt. %) (wt. %) % (wt. %) (g) (wt. %) (months) 12 LV-2 2 × 52.3214.61 0.19 20.00 12.87 80.7 32.97 1282 37.3 2.5 TBA 13 LV-2 2 × 52.3214.61 0.19 20.00 12.87 80.7 32.97 1282 37.3 4.5 OX 14 LV-2 2 × 52.3214.61 0.19 20.00 12.87 80.7 32.97 1282 37.3 2.5 PC 15 LV-2 52.32 14.610.19 20.00 3.86 9.02 80.7 32.97 1282 37.3 4.0 PC-TBA 16 LV-2 52.32 14.610.19 20.00 3.86 9.02 80.7 32.97 1282 37.3 4.0 PC-OX 17 LV-2 2 × 50.3814.07 0.19 19.26 7.43 8.68 80.7 31.20 1282 35.3 4.0 PC-TBA 18 LV-2 51.9514.51 0.19 19.86 9.66 3.83 80.7 32.63 1282 51.0 9.0+ PC-MAK 19 LV-2 2 ×50.38 14.07 0.19 19.26 2.41 7.43 6.27 80.7 31.20 1282 38.7 na PC-TBA-MAK 20 LV-2 2 × 48.91 13.66 0.18 18.69 2.92 7.21 8.43 80.7 29.89 128238.0 na PC-TBA- DPM 21 2 Stand- 52.32 14.61 0.19 20.00 3.86 9.02 80.732.97 1282 56.2 6.0+ ard

TABLE 9 Low VOC LV-2 Final Formulations by Weight Composition Dipro-Para- pylene chloro- Glycol Methyl Propyl- benzo- tert Poly- Col- Sul-Methyl Amyl ene Car- trifluoride Butyl Hy- Pro- Stable sil- loidal furicEthanol Ether Ketone bonate (PCBTF) Acetate drol- duct Atmos- icatesSilica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO₂ VOC phericBinder (g) (g) (g) (g) (g) (g) (g) (g) (g) % (wt. %) (wt. %) (months) 12LV-2 2 × TBA 890.4 292.3 7.8 1012.9 515.0 80.7 32.97 37.3 2.5 13 LV-2 2× OX 890.4 292.3 7.8 1012.9 515.0 80.7 32.97 37.3 4.5 14 LV-2 2 × PC890.4 292.3 7.8 1012.9 515.0 80.7 32.97 37.3 2.5 15 LV-2 PC-TBA 890.4292.3 7.8 1012.9 154.3 360.7 80.7 32.97 37.3 4.0 16 LV-2 PC-OX 890.4292.3 7.8 1012.9 154.3 360.7 80.7 31.20 35.3 4.0 17 LV-2 2 × 890.4 292.37.8 1012.9 308.6 360.7 80.7 31.20 35.3 4.0 PC-TBA 18 LV-2 PC-MAK 890.4292.3 7.8 1012.9 389.2 154.3 80.7 32.62 51.0 9.0+ 19 LV-2 2 × 890.4292.3 7.8 1012.9 100.0 308.6 260.7 80.7 31.20 38.7 na PC-TBA-MAK 20 LV-22 × 890.4 292.3 7.8 1012.9 125.0 308.6 360.7 80.7 29.89 38.0 naPC-TBA-DPM 21 2 Standard 890.4 292.3 7.8 1012.9 154.3 360.7 80.7 32.9756.2 6.0+

TABLE 10 Low VOC LV-2 Final Product Formulations Percent CompositionDipro- Para- pylene chloro- Glycol Methyl Propyl- benzo- tert Poly- Col-Sul- Methyl Amyl ene Car- trifluoride Butyl Hy- Pro- Stable sil- loidalfuric Ethanol Ether Ketone bonate (PCBTF) Acetate drol- duct Atmos-icates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO₂ VOCpheric Binder (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %)(wt. %) (wt. %) % (wt. %) (wt. %) (months) 12 LV-2 2 × TBA 32.75 10.750.29 37.26 18.94 80.7 32.97 37.3 2.5 13 LV-2 2 × OX 32.75 10.75 0.2937.26 18.94 80.7 32.97 37.3 4.5 14 LV-2 2 × PC 32.75 10.75 0.29 37.2618.94 80.7 32.97 37.3 2.5 15 LV-2 PC-TBA 32.75 10.75 0.29 37.26 5.6813.27 80.7 32.97 37.3 4.0 16 LV-2 PC-OX 32.75 10.75 0.29 37.26 5.6813.27 80.7 32.97 37.3 4.0 17 LV-2 2 × 31.00 10.18 0.27 35.26 10.74 12.5680.7 31.20 35.3 4.0 PC-TBA 18 LV-2 PC-MAK 32.41 10.64 0.28 36.87 14.175.62 80.7 32.62 51.0 9.0+ 19 LV-2 2 × 31.00 10.18 0.27 35.26 3.48 10.749.08 80.7 31.20 38.7 na PC-TBA-MAK 20 LV-2 2 × 29.70 9.75 0.26 33.794.17 10.29 12.03 80.7 29.89 38.0 na PC-TBA-DPM 21 2 Standard 32.75 10.750.29 37.26 5.68 13.27 80.7 32.97 56.2 6.0+As stated above, the ethylsilicate polymer may be a binder used ininorganic zinc rich primers. For an exemplary product using the binderof the present invention, lower regulated VOC levels are achievable,while maintaining desired performance characteristics. As providedbelow, normal cure primers, which typically means a cure time in excessof twelve hours and more likely closer to twenty-four hours, havevarious test data regarding the performance characteristics in Table 11below. Examples 12-17 have been included from Tables 7-10, as well asthe control sample of a standard binder not using the present invention,which was Example 21. In addition, new Examples 22-25 are included whereExample 22 is similar to Example 13, but the PCBTF (refers to the OX inthe chart) is a single, not double amount, Example 23 is similar toExample 14, but includes half of the PC, Example 24 is similar toExample 12, but includes half of the TBA of Example 12, and Example 25is different form the other examples, as it uses a combination of PCBTFand TBA as replacement solvents. Example 25 has a specific makeup due tothe fact no exempt solvent is added to the reaction after hydrolysis andbefore stripping, the PCBTF and TBA are added after the ethanol strip.As seen in Table 11, Example 21 is the control sample of one exemplaryprior binder, as discussed above, and with the exception of the binderin Example 22 (at the top of Table 11), the performance characteristicsare similar to the control samples of Example 21 after 48 hours of curetime. The rub test is generally an industry standard solvent resistancerub test, such as ASTM D4752 or NCCA11-18, used to determine the degreeof cure of a thin (not baked) film by the coating film resistance to aspecified solvent. In the rub test used in Table 11, the solvent ismethyl ethyl ketone (MEK) and a cheesecloth is cloaked in MEK andstroked across the surface for a specified stroke distance, rate andpressure. In Table 11, a test standard of fifty double rubs were usedfor the number of strokes. Similarly, the cross hatch test is a standardtest method for measuring adhesion by tape test, where a cross hatchpatter is made through an applied film to a substrate and pressuresensitive tape is applied over the area of incisions. The tape is thenremoved rapidly, such as specified in ASTM D 3359. Similarly, the pencilhardness test is a commonly used industry test similar to a scratchtest, where harder and harder pencils are used until the coating isscratched, with the softest pencil lead scratching the surface being thehardness. Therefore, the 6H refers to the hardness of the pencil leadand is the maximum pencil hardness used in the test method.

TABLE 11 LV-2 Normal Cure Time Paint Trials Trial # 2 Trial # 2 Trial #2 Trial # 1 Trial # 1 Trial # 1 Low VOC Gel Calc. 50 Rub Pencil Cross 50Rub Pencil Cross Stable Binders Analysis SiO₂ Time Product MEK TestHatch MEK Test Hatch Binder Date of Trial Number Page # Wt. % (sec) VOC% (24 hrs) (24 hrs) (24 hrs) (48 hrs) (48 hrs) (48 hrs) 22 LV-2 OX Mar.6, 2013 158150 B42P31 33.2 209 31.5 13 6H 2-3 13 LV-2 2 × OX Apr. 9,2013 158995 B42P37 32.9 124 37.3 50 6H 4 50 6H 3 23 XHT-28LV-PC Mar. 20,2013 158452 B42P35 32.2 67 31.5 48 6H 4-5 14 LV-2 2 × PC Apr. 3, 2013158827 B42P36 33.1 44 37.3 50 6H 3 50 6H 5 24 LV-2 TBA Mar. 20, 2013158492 B42P35 31.9 68 31.5 50 6H 4 50 6H 4-5 12 LV-2 2 × TBA Apr. 12,2013 159064 B42P38 33.0 42 37.3 50 H 1-2 16 LV-2 PC-OX Apr. 15, 2013159146 B42P40 31.7 59 37.3 50 6H 4 50 6H 3-4 17 LV-2 PC-OX Mar. 22, 2013158495 B44P29 31.9 61 37.3 50 6H 4 50 6H 5 25 LV-2 OX-TBA Mar. 22, 2013158494 B44P29 32.0 58 37.3 50 6H 4 50 6H 3-4 15 LV-2 PC-TBA Mar. 22,2013 158496 B44P29 32.0 60 37.3 50 6H 1-2 21 Control # 1 Mar. 22, 2013158856 32.8 47 56.2 50 6H 3-4 46 6H 5 Standard 2 21 Control # 2-1 Mar.22, 2013 158856 32.8 47 56.2 50 6H 3 Standard 2 21 Control # 2-2 Mar.22, 2013 158856 32.8 47 56.2 50 6H 3 Standard 2 Pass MEK Rub Test 50Cross Hatch 3B-5B Pencil Test 4H-6H

Certain of the examples were surprisingly found to have a fast curetime, faster than the control sample. As illustrated in Table 12, thefast cure time binders, Examples 15, 16 and 18, which are also found inTables 7-10, had similar performance, with Example 15 even at six hoursshowing what required at least twice as long for the control sample inExample 21. Out-performing the control sample.

TABLE 12 Fast Cure Paint Trials LV-2 and Standard 2 6 Hour Test Data 8Hour Test Data Solvent Rub Pencil Cross Rub Pencil Cross CombinationTrial Date Analysis # Test Test Hatch Trial Date Analysis # Test TestHatch 18 LV-2 PC/MAK Jan. 17, 2014 5 3H 2B Jan. 17, 2014 9 4H 4B 16 LV-2PC/OX Jan. 17, 2014 4 4H 2B Jan. 17, 2014 5 6H 3B 15 LV-2 PC/TBA Jan.17, 2014 50 6H 5B Jan. 17, 2014 50 6H 5B 21 Standard 2 Jan. 17, 2014163267 9 5H 4B Jan. 17, 2014 163267 11 5H 4B 12 Hour Test Data 24 HourTest Data Solvent Rub Pencil Cross Rub Pencil Cross Combination TrialDate Analysis # Test Test Hatch Trial Date Analysis # Test Test Hatch 18LV-2 PC/MAK Jan. 17, 2014 33 6H 4B Jan. 18, 2014 50 6H 5B 16 LV-2 PC/OXJan. 17, 2014 5 5H 3B Jan. 18, 2014 24 6H 4B 15 LV-2 PC/TBA Jan. 17,2014 50 6H 5B Jan. 18, 2014 50 6H 5B 21 Standard 2 Jan. 17, 2014 16326750 6H 4B Jan. 18, 2014 163267 50 6H 5B Pass MEK Rub Test 50 Cross Hatch3B-5B Pencil Test 4H-6H Fast Cure less than 12 hours

Tables 13-17 also show variations of the LV-3 batches, which areprovided as Examples 1-10 plus control sample in Example 11 in Tables 3and 4. The examples are numbered in Tables 13-17 and are sufficient toshow that they meet the desired performance characteristics relative tothe control sample. In addition, six tests were performed on differentruns of the sample examples to provide a wide range of data. The LV-3batches with PC/TBA samples 3-5 demonstrate fully cured at 6 hours vs 12and 24 hour fully cured for the Standard 3 control, sample 11.

TABLE 13 LV-3 Paint Trials Comparison 4 Hour Cure Test Data Solvent RubPencil Cross Combination Trial Date Analysis # Test Test Hatch  1 LV-3PC/PC Sept. 2, 2013 162054 17 4B 2B  1 LV-3 PC/PC Sept. 10, 2013 1620546 6B 0B  1 LV-3 PC/PC Sept. 30, 2013 162054 3 4B 3B  1 LV-3 PC/PC Oct.1, 2013 162054 13 4B 3B  1 LV-3 PC/PC Oct. 2, 2013 162054 11 F 3B  1LV-3 PC/PC Oct. 17, 2013 162054 6 4B 4B  2 LV-3 PC/OX Sept. 2, 2013162055 34 6H 4B  2 LV-3 PC/OX Sept. 10, 2013 162055 6 2H 4B  2 LV-3PC/OX Sept. 30, 2013 162055 4 2H 3B  2 LV-3 PC/OX Oct. 1, 2013 162055 195H 5B  2 LV-3 PC/OX Oct. 2, 2013 162055 50 6H 5B  2 LV-3 PC/OX Oct. 17,2013 162055 9 HB 3B  3 LV-3 PC/TBA Sept. 2, 2013 162389 16 5H 4B  3 LV-3PC/TBA Sept. 10, 2013 162389 26 6H 4B  3 LV-3 PC/TBA Sept. 30, 2013162389 12 6H 5B  3 LV-3 PC/TBA Oct. 1, 2013 162389 50 6H 5B  3 LV-3PC/TBA Oct. 2, 2013 162389 24 5H 5B  3 LV-3 PC/TBA Oct. 17, 2013 16238950 6H 5B  3 LV-3 PC/TBA  4 LV-3 2 × PC/TBA  5 LV-3 PC/TBA Inc Acid 11 3Standard Control Sept. 2, 2013 160974 32 6H 3B 11 3 Standard ControlSept. 10, 2013 160974 6 2H 2B 11 3 Standard Control Sept. 30, 2013160974 3 6B 2B 11 3 Standard Control Oct. 1, 2013 160974 11 B 2B 11 3Standard Control Oct. 2, 2013 160974 20 F 4B 11 3 Standard Control Oct.17, 2013 160974 4 3B 3B 11 3 Standard Control na na na na na

TABLE 14 LV-3 Paint Trials Comparison 6 Hour Cure Test Data Solvent RubPencil Cross Combination Trial Date Analysis # Test Test Hatch  1 LV-3PC/PC Sept. 2, 2013 162054 50 4H 3B  1 LV-3 PC/PC Sept. 10, 2013 1620544 4B 2B  1 LV-3 PC/PC Sept. 30, 2013 162054 7 2B 3B  1 LV-3 PC/PC Oct.1, 2013 162054 12 3H 4B  1 LV-3 PC/PC Oct. 2, 2013 162054 16 6H 5B  1LV-3 PC/PC Oct. 17, 2013 162054 9 2H 4B  2 LV-3 PC/OX Sept. 2, 2013162055 34 6H 5B  2 LV-3 PC/OX Sept. 10, 2013 162055 8 5H 4B  2 LV-3PC/OX Sept. 30, 2013 162055 5 5H 4B  2 LV-3 PC/OX Oct. 1, 2013 162055 326H 4B  2 LV-3 PC/OX Oct. 2, 2013 162055 50 6H 5B  2 LV-3 PC/OX Oct. 17,2013 162055 12 H 5B  3 LV-3 PC/TBA Sept. 2, 2013 162389 37 6H 4B  3 LV-3PC/TBA Sept. 10, 2013 162389 48 6H 4B  3 LV-3 PC/TBA Sept. 30, 2013162389 50 6H 5B  3 LV-3 PC/TBA Oct. 1, 2013 162389 50 6H 5B  3 LV-3PC/TBA Oct. 2, 2013 162389 50 6H 5B  3 LV-3 PC/TBA Oct. 17, 2013 16238950 6H 5B  3 LV-3 PC/TBA Jan. 17, 2014 164338 50 6H 5B  4 LV-3 2 × PC/TBAJan. 17, 2014 1300490 27 4H 5B  5 LV-3 PC/TBA Jan. 17, 2014 1300308 506H 5B Inc Acid 11 3 Standard Control Sept. 2, 2013 160974 42 6H 4B 11 3Standard Control Sept. 10, 2013 160974 10 6H 5B 11 3 Standard ControlSept. 30, 2013 160974 5 3B 3B 11 3 Standard Control Oct. 1, 2013 16097439 5H 4B 11 3 Standard Control Oct. 2, 2013 160974 25 4H 5B 11 3Standard Control Oct. 17, 2013 160974 7 HB 3B 11 3 Standard Control Jan.17, 2014 131902251 4 2B 1B

TABLE 15 LV-3 Paint Trials Comparison 8 Hour Cure Test Data Solvent RubPencil Cross Combination Trial Date Analysis # Test Test Hatch  1 LV-3PC/PC Sept. 2, 2013 162054 ND ND ND  1 LV-3 PC/PC Sept. 10, 2013 16205412 B 2B  1 LV-3 PC/PC Sept. 30, 2013 162054 4 B 4B  1 LV-3 PC/PC Oct. 1,2013 162054 13 2H 4B  1 LV-3 PC/PC Oct. 2, 2013 162054 32 6H 5B  1 LV-3PC/PC Oct. 17, 2013 162054 5 6H 4B  2 LV-3 PC/OX Sept. 2, 2013 162055 NDND ND  2 LV-3 PC/OX Sept. 10, 2013 162055 26 5H 5B  2 LV-3 PC/OX Sept.30, 2013 162055 9 6H 4B  2 LV-3 PC/OX Oct. 1, 2013 162055 41 6H 5B  2LV-3 PC/OX Oct. 2, 2013 162055 50 6H 5B  2 LV-3 PC/OX Oct. 17, 2013162055 6 6H 5B  3 LV-3 PC/TBA Sept. 2, 2013 162389 ND ND ND  3 LV-3PC/TBA Sept. 10, 2013 162389 50 6H 5B  3 LV-3 PC/TBA Sept. 30, 2013162389 50 6H 5B  3 LV-3 PC/TBA Oct. 1, 2013 162389 50 6H 5B  3 LV-3PC/TBA Oct. 2, 2013 162389 50 6H 5B  3 LV-3 PC/TBA Oct. 17, 2013 16238950 6H 5B  3 LV-3 PC/TBA Jan. 17, 2014 164338 50 6H 5B  4 LV-3 2 × PC/TBAJan. 17, 2014 1300490 50 4H 5B  5 LV-3 PC/TBA Jan. 17, 2014 1300308 506H 5B Inc Acid 11 3 Standard Control Sept. 2, 2013 160974 ND ND ND 11 3Standard Control Sept. 10, 2013 160974 50 6H 5B 11 3 Standard ControlSept. 30, 2013 160974 5 HB 3B 11 3 Standard Control Oct. 1, 2013 16097450 6H 4B 11 3 Standard Control Oct. 2, 2013 160974 12 6H 5B 11 3Standard Control Oct. 17, 2013 160974 8 5H 4B 11 3 Standard Control Jan.17, 2014 131902251 4 HB 2B

TABLE 16 LV-3 Paint Trials Comparison 12 Hour Cure Test Data Solvent RubPencil Cross Combination Trial Date Analysis # Test Test Hatch  1 LV-3PC/PC Sept. 2, 2013 162054 50 6H 5B  1 LV-3 PC/PC Sept. 10, 2013 1620547 3H 2B  1 LV-3 PC/PC Sept. 30, 2013 162054 16 6H 4B  1 LV-3 PC/PC Oct.1, 2013 162054 18 3H 4B  1 LV-3 PC/PC Oct. 2, 2013 162054 40 6H 5B  1LV-3 PC/PC Oct. 17, 2013 162054 17 6H 4B  2 LV-3 PC/OX Sept. 2, 2013162055 50 6H 5B  2 LV-3 PC/OX Sept. 10, 2013 162055 19 6H 4B  2 LV-3PC/OX Sept. 30, 2013 162055 22 4H 4B  2 LV-3 PC/OX Oct. 1, 2013 16205550 6H 5B  2 LV-3 PC/OX Oct. 2, 2013 162055 50 6H 5B  2 LV-3 PC/OX Oct.17, 2013 162055 34 6H 5B  3 LV-3 PC/TBA Sept. 2, 2013 162389 50 6H 4B  3LV-3 PC/TBA Sept. 10, 2013 162389 50 6H 5B  3 LV-3 PC/TBA Sept. 30, 2013162389 50 6H 5B  3 LV-3 PC/TBA Oct. 1, 2013 162389 50 6H 5B  3 LV-3PC/TBA Oct. 2, 2013 162389 50 6H 5B  3 LV-3 PC/TBA Oct. 17, 2013 16238950 6H 5B  3 LV-3 PC/TBA Jan. 17, 2014 164338 50 6H 5B  4 LV-3 2 × PC/TBAJan. 17, 2014 1300490 50 4H 5B  5 LV-3 PC/TBA Jan. 17, 2014 1300308 506H 5B Inc Acid 11 3 Standard Control Sept. 2, 2013 160974 50 5H 4B 11 3Standard Control Sept. 10, 2013 160974 50 6H 5B 11 3 Standard ControlSept. 30, 2013 160974 27 6H 4B 11 3 Standard Control Oct. 1, 2013 16097450 6H 5B 11 3 Standard Control Oct. 2, 2013 160974 50 6H 5B 11 3Standard Control Oct. 17, 2013 160974 22 6H 4B 11 3 Standard ControlJan. 17, 2014 131902251 23 2H 3B

TABLE 17 LV-3 Paint Trials Comparison 24 Hour Cure Test Data Solvent RubPencil Cross Combination Trial Date Analysis # Test Test Hatch  1 LV-3PC/PC Sept. 2, 162054 50 6H 5B 2013  1 LV-3 PC/PC Sept. 10, 162054 50 6H5B 2013  1 LV-3 PC/PC Sept. 30, 162054 50 6H 5B 2013  1 LV-3 PC/PC Oct.1, 162054 50 6H 5B 2013  1 LV-3 PC/PC Oct. 2, 162054 50 6H 5B 2013  1LV-3 PC/PC Oct. 17, 162054 50 6H 5B 2013  2 LV-3 PC/OX Sept. 2, 16205550 6H 5B 2013  2 LV-3 PC/OX Sept. 10, 162055 50 6H 5B 2013  2 LV-3 PC/OXSept. 30, 162055 50 6H 5B 2013  2 LV-3 PC/OX Oct. 1, 162055 50 6H 5B2013  2 LV-3 PC/OX Oct. 2, 162055 50 6H 5B 2013  2 LV-3 PC/OX Oct. 17,162055 50 6H 5B 2013  3 LV-3 PC/TBA Sept. 2, 162389 50 6H 5B 2013  3LV-3 PC/TBA Sept. 10, 162389 50 6H 5B 2013  3 LV-3 PC/TBA Sept. 30,162389 50 6H 5B 2013  3 LV-3 PC/TBA Oct. 1, 162389 50 6H 5B 2013  3 LV-3PC/TBA Oct. 2, 162389 50 6H 5B 2013  3 LV-3 PC/TBA Oct. 17, 162389 50 6H5B 2013  3 LV-3 PC/TBA Jan. 17, 164338 50 6H 5B 2014  4 LV-3 2 × Jan.17, 1300490 50 6H 5B PC/TBA 2014  5 LV-3 PC/TBA Jan. 17, 1300308 50 6H5B Inc Acid 2014 11 3 Standard Control Sept. 2, 160974 50 6H 5B 2013 113 Standard Control Sept. 10, 160974 50 6H 5B 2013 11 3 Standard ControlSept. 30, 160974 50 6H 5B 2013 11 3 Standard Control Oct. 1, 160974 506H 5B 2013 11 3 Standard Control Oct. 2, 160974 50 6H 5B 2013 11 3Standard Control Oct. 17, 160974 50 6H 5B 2013 11 3 Standard ControlJan. 17, 131902251 50 6H 4B 2014 Pass MEK Rub Test 50 Cross Hatch 3B-5BPencil Test 4H-6H Note: Fast Cure is less than 12 hours Standard cure is12 to 24 hours

TABLE 18 Dipro- pylene Parachloro- Glycol Methyl Propyl- benzo- tertCol- Sul- Methyl Amyl ene Car- trifluoride Butyl Pro- Stable Poly-loidal furic Ethanol Ether Ketone bonate (PCBTF) Acetate Hydrol- ductAtmos- silicates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA)ysis SiO₂ VOC pheric Binder (g) (g) (g) (g) (g) (g) (g) (g) (g) % (wt.%) (wt. %) (months) LV-4 PC 1043.1 235.4 9.4 2215.1 397 67.6 20.92 56.8na LV-5 PC 2495.0 0 3.6 1333.7 200 86.0 24.12 52.2 na LV-5 PC ½Ethanol2495.0 0 3.6 666.8 200 86 28.67 43.1 na LV-3.1 (Theoretical) 6160.01400.0 24.0 5440.0 1500 1500 67.9 30.20 33.9 na

TABLE 19 lene Parachloro- Glycol Methyl Propyl- benzo- tert Poly- Col-Sul- Methyl Amyl ene Car- trifluoride Butyl Hy- Pro- Stable sil- loidalfuric Ethanol Ether Ketone bonate (PCBTF) Acetate drol- duct Atmos-icates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO₂ VOCpheric Binder (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %)(wt. %) (wt. %) % (wt. %) (wt. %) (months) LV-4 PC 26.75 6.04 0.24 56.8010.18 0.00 67.6 20.92 56.8 na LV-5 PC 43.00 0 0.09 52.18 4.76 0.00 8624.12 52.2 na LV-5 PC ½Ethanol 51.09 0.1 43.15 5.66 28.67 43.1 na LV-3.1(Theoretical) 38.44 8.74 0.15 33.95 9.36 9.36 67.9 30.20 33.9 na

TABLE 20 Product Stable SiO_(2.) VOC Atmospheric Binder ₍wt. %) (wt. %)(months) Silbond HT-28A 32.97 56.2 6.0+ Silbond HT-33 33.56 50.5 6.0+Silbond HT-21.5PM 20.08 74.4 6.0+ Silbond H-25 25.32 54.8 6.0+ SilbondHT-30 30.2 52.7 6.0+

As described above, the ethylsilicate composition in Tables 18 and 19are specifically configured for the casting industry, although theycould be used in the coatings industry, and the LV3.1 is applicable toboth industries. The compositions have been found to provide fasterset-up times and create a harder ceramic material in the investmentcasting process. It should be noted that in all the tables, the columnidentified as Product VOC, is the amount of regulated VOCs, the totalVOCs may be higher. In regards to Table 20, these are existing bindersmade by Silbond, and the amount of regulated VOCs, amount of silica andstability may be seen for comparison. While the casting binders inTables 18-19 have higher regulated VOCs than some of the other binders,casting binders have always had higher regulated VOCs, and the newcompositions are substantially reduced as compared to the prior art.

The procedure for making the binders generally includes charging ethanoland sulfuric acid, if desired colloidal silica sol, heating the reactor,an ethylsilicate is added to the reactor, which is the hydrolysisreaction, additional heat may be applied to the reactor, if desiredethanol is stripped from the reactor, then the reactor is cooled, chargeat least one of the exempt solvents and or a non-exempt to the reactor,mix and then package.

More specifically, Example 16 from Tables 7-10 may be formed as follows.First, charge 800.0 g of ethanol and 7.8 g of sulfuric acid in thereactor and mix for 20 minutes. Then Charge 584.6 g of colloidal silicasol to the reactor (colloidal silica sol is 50% sodium silicatedispersion) and heat reactor to 40 degrees C. Meter in slowly 2093 g ofethylsilicates via a dip tube. This is the hydrolysis reaction, which inthis formulation produces 1494.9 g of ethanol. Heat to 78 degrees C. andreflux for sixty minutes. If desired, strip ethanol from the reactor, inthis example 1282 g of ethanol stripped which is 55% of total ethanolafter the hydrolysis. The reactor is then cooled for thirty minutesafter which 360.7 g of PCBT (Oxsol 100) is added to the reactor, alongwith 154.3 g of PC (Propylene Carbonate). The PCBT and PC are mixed infor 30 minutes and the final product is packaged as desired.

In the above example, 1494.9 g of ethanol is produced during hydrolysis.

More specifically, Example 3 from Tables 3-6 may be formed as follows.First, charge 537.6 g of colloidal silica sol to the reactor (colloidalsilica sol is 50% sodium silicate dispersion) and 10.6 g of sulfuricacid in the reactor and immediately charge 179.8 g of PC (PropyleneCarbonate) to the reactor. Start full cooling on the reactor. Meter in917.4 g of ethylsilicates via a dip tube. This is the hydrolysisreaction, which in this formulation produces 1374.7 g of ethanol. Add1313.5 g of ethylsilicates to the reactor. Add 497.6 g of ethylsilicatesto the reactor. Allow contents to mix for one hour and adjust reactortemperature to 30-50 degree C. After one hour, add 389.2 g of TBA (tertbutyl acetate) is added to the reactor. Mix for 30 minutes and maintainreactor of 30-40 degree C. The final product is packaged as desired. Theadded ethylsilicates may vary with different polyethylsilicates, andhave different amounts of hydrolysis when added.

In the above example, 1374.7 g of ethanol is produced during hydrolysis.

The procedure for making the LV-5 PC, with half the normal Ethanol is asfollows. First, charge 666.8 g of ethanol to reactor, add 3.6 g ofsulfuric acid to the reactor, add 2495 g of polysilicates to thereactor, and add 200 g of PC (Propylene Carbonate) to the reactor. Heatreactor to 25-45° C., preferably 30-40° C. Hydrolyze into the reactormixture 167.7 g of water dropwise using an addition funnel. After thewater addition is completed, mix for 60 minutes and maintain reactor of30-40 degree C. After 60 minutes, allow the binder to cure. The finalproduct is packaged as desired. Take a pint sample to the Analytical Labfor analysis. It should be noted for all the above examples, thetemperature and times may vary, such as lowering the temperature mayjust take longer for the method to complete, and increasing thetemperature may speed up the method.

While the invention has been described in connection with its preferredembodiments it should be recognized that changes and modifications maybe made therein without departing from the scope of appended claims.

1. A polyethylsilicate composition comprising: 18-50% by weight SiO₂based on the total composition weight; 0-60% by weight alcohol based onthe total composition weight; and a positive amount of solvent, whereinsaid solvent forms up to 40% by weight, based on the total compositionweight, and wherein said solvent comprises at least one of propylenecarbonate, tert-butylacetate, 2-amino 2-methyl 1-proponal, orparachlorobenzotrifluoride; and wherein said solvent and said alcohol incombination comprise 5-70% by weight, based on the total compositionweight.
 2. The composition of claim 1 wherein the ethylsilicatecomposition is hydrolyzed in an amount of 55-90%.
 3. The composition ofclaim 1 wherein ethanol forms the majority of said alcohol.
 4. Thecomposition of claim 3 wherein said alcohol is substantially ethanol. 5.The composition of claim 3 wherein said solvent and said ethanol are10-55% by weight, based on the weight of the total composition.
 6. Thecomposition of claim 5 wherein said solvent and said ethanol comprise16-45% by weight, based on the weight of the total composition.
 7. Thecomposition of claim 6 wherein said solvent and said ethanol comprise35-50% by weight, based on the weight of the total composition.
 8. Thecomposition of claim 5 wherein said solvent and said ethanol comprise10-70% by weight, based on the weight of the total composition.
 9. Thecomposition of claim 8 wherein said solvent and said ethanol comprise30-68% by weight, based on the weight of the total composition.
 10. Thecomposition of claim 9 wherein said solvent and said ethanol comprise40-60% by weight, based on the weight of the total composition.
 11. Thecomposition of claim 3 wherein said ethanol is less than 60% by weight,based on the weight of the total composition.
 12. The composition ofclaim 11 wherein said ethanol is less than 45% by weight, based on theweight of the total composition.
 13. The composition of claim 12 whereinsaid ethanol is 10-40% by weight, based on the weight of the totalcomposition.
 14. The composition of claim 1 wherein said solventincludes less than 10% by weight of methyl amyl ketone, based on thetotal weight of the composition, and less than 7.5% by weight ofdipropylene glycol methyl ether, based on the total weight of thecomposition.
 15. The composition of claim 14 wherein said solventincludes less than 5% by weight of said methyl amyl ketone and saiddipropylene glycol methyl ether in combination, based on the totalweight of the composition.
 16. The composition of claim 14 wherein saidsolvent includes less than 3% by weight of said methyl amyl ketone andsaid dipropylene glycol methyl ether in combination, based on the totalweight of the composition.
 17. The composition of claim 14 wherein saidsolvent includes less than 1-3% by weight of said methyl amyl ketone andsaid dipropylene glycol methyl ether, based on the total weight of thecomposition.
 18. The composition of claim 17 wherein said ethylsilicatecomposition is essentially free of said methyl amyl ketone and saiddipropylene glycol methyl ether.
 19. The composition of claim 1 whereinsaid solvent includes at least one of 0-25% by weight of said propylenecarbonate, 0-25% by weight of said tert-butylacetate, or 0-25% by weightof said parachlorobenzotrifluoride, each individually based upon thetotal weight of the composition.
 20. The composition of claim 19 whereinsaid solvent includes 5-15% by weight of said propylene carbonate, basedon the total weight of the composition.
 21. The composition of claim 20wherein said solvent includes 5-10% by weight of said propylenecarbonate based on the total weight of the composition.
 22. Thecomposition of claim 19 wherein said solvent includes 5-18% by weight ofsaid tert-butylacetate, based on the total weight of the composition.23. The composition of claim 16 wherein said solvent includes 8-15% byweight of said tert-butylacetate, based on the total weight of thecomposition.
 24. The composition of claim 13 wherein said solventincludes 5-15% by weight of said parachlorobenzotrifluoride, based onthe total weight of the composition.
 25. The composition of claim 13wherein said solvent includes 8-15% by weight of saidparachlorobenzotrifluoride based on the total weight of the composition.26. The composition of claim 1 wherein said solvent comprise 3-40% byweight of the total composition.
 27. The composition of claim 1 whereinsaid solvent comprise 4-30% by weight of the total composition.
 28. Thecomposition of claim 1 wherein said solvent comprise 4-24% by weight ofthe total composition.
 29. The composition of claim 1 wherein anyindividual component of said solvent does not form more than 30% byweight of the total weight of the composition.
 30. The composition ofclaim 1 wherein said solvent includes said propylene carbonate and saidtert-butylacetate.
 31. The composition of claim 30 wherein said solventincludes 10-25% by weight of the combination of said propylene carbonateand said tert-butylacetate, based on the total weight of thecomposition.
 32. The composition of claim 31 wherein said solventincludes 10-20% by weight of said propylene carbonate and 5-15% byweight of said tert-butylacetate, each based on the total weight of thecomposition.
 33. The composition of claim 31 wherein said solventincludes 3-12% by weight of said propylene carbonate and 7-14% by weightof said tert-butylacetate, each based on the total weight of thecomposition.
 34. The composition of claim 31 wherein said solventincludes 5-6% by weight of said propylene carbonate and 13-14% by weightof said tert-butyl-acetate each based on the weight of the totalcomposition.
 35. The composition of claim 34 wherein said alcohol forms35-40% by weight, based on the total weight of the composition.
 36. Thecomposition of claim 1 added to zinc particles and refractories to forma zinc rich coating and wherein the zinc rich coating when applied to asurface is capable of passing a MEK 50 rub test within six to eighthours after application to the surface.
 37. The composition of claim 30wherein said alcohol is 35-40% by weight, said solvents are 18-20% byweight and include 5-6% by weight of said propylene carbonate and 13-14%by weight of said tert-butyl-acetate, each based upon the total weightof the composition.
 38. The composition of claim 24 wherein saidethylsilicate is hydrolyzed and wherein said propylene carbonate isadded before or during hydrolysis and said tert-butyl-acetate is addedafter hydrolysis.
 39. The composition of claim 1 wherein said SiO₂ is acolloidal silica sol.
 40. The composition of claim 1 wherein said SiO₂is a condensed silica solution.
 41. An polyethylsilicate compositioncomprising: 18-80% by weight of SiO₂, based on the total weight of thecomposition; an acid; an alcohol; and propylene carbonate in an amountof up to 30% by weight, based on the total weight of the composition andwherein said alcohol and said propylene carbonate in combination formless than 70% by weight, based on the total weight of the composition.42. The composition of claim 41 wherein the composition is hydrolyzed inan amount of 55-90%, and wherein said propylene carbonate is addedbefore hydrolization of the composition.
 43. The composition of claim 42further including tert-butylacetate added after hydrolysis.
 44. Thecomposition of claim 41 further including parachlorobenzotrifluoride inan amount of up to 25% by weight, based on the total weight of thecomposition.
 45. The composition of claim 44 further includingtert-butylacetate in an amount of up to 25% by weight, based on thetotal weight of the composition.
 46. The composition of claim 45 whereinin combination, said tert-butylacetate, said parachlorobenzotrifluorideand said propylene carbonate form 5-40% by weight, based on the totalweight of the composition.
 47. A method of forming a polyethylsilicatecomposition wherein said method includes the steps of: adding anethanol, an acid and a silica source to a reactor; heating the reactorafter said step of adding; adding an ethylsilicate source to the reactorto initiate a hydrolysis reaction; and adding propylene carbonate to thereactor after the hydrolysis reaction.
 48. The method of claim 47further including the steps of adding parachlorobenzotrifluoride to thereactor after the hydrolysis reaction.
 49. The method of claim 47further including a step of stripping ethanol from the reactor after thehydrolysis reaction.
 50. The method of claim 47 wherein said silicasource is a colloidal silica sol.
 51. The method of claim 47 furtherincluding a step of adding propylene carbonate before said step ofadding an ethylsilicate source.
 52. The method of claim 47 furtherincluding a step of adding a propylene carbonate during said step ofadding an ethylsilicate source.
 53. The method of claim 47 furtherincluding a step of adding a polyethylsilicate source.
 54. A method offorming a polyethylsilicate composition and wherein said method includesthe steps of: adding a silica source and a propylene carbonate to areactor; and adding an ethylsilicate source to the reactor to initiate ahydrolysis reaction.
 55. The method of claim 54 further including thestep of adding tert-butylacetate to the reactor after said hydrolysisreaction.
 56. The method of claim 54 further including the step ofadding additional propylene carbonate after said hydrolysis reaction.57. The method of claim 54 further including the steps of: adding amineral acid to the reactor before said hydrolysis reaction; adding asolvent after said hydrolysis reaction, said solvent selected from thegroup consisting of propylene carbonate, tert-butylacetate, andparachlorobenzotrifluoride; and adding a polyethylsilicate after saidhydrolysis reaction.
 58. A method of forming a polyethylsilicatecomposition wherein said method includes the steps of: adding ethanol,an acid and a silica source, and propylene carbonate to a reactor;heating the reactor after said step of adding; and hydrolizing thecontents of the reactor.
 59. The method of claim 59 wherein said step ofhydrolizing the contents of the reactor further includes the step ofadding water to the reactor.
 60. The method of claim 58 wherein saidsilica source is a polyethylsilicate.